Photographic developing process with amino hydroxy cycloalkenone

ABSTRACT

PHOTOGRAPHIC SILVER HALIDE DEVELOPING AGENTS WHICH ARE AMINO HYDROXY CYCLOALKENONE COMPOUNDS HAVING A FIVE OR SIX MEMBER CYCLOALKENE NUCLEUS PROVIDE INCREASED DEVELOPMENT ACTIVITY, E.G. REDUCED DEVELOPMENT TIME, AND PROVIDE LOW-COLORED OXIDATION PRODUCTS WITHOUT UNDESIRED SENSITOMETRIC PROPERTIES IN DEVELOPING A LATENT IMAGE IN A PHOTOGRAPHIC ELEMENT. THESE DEVELOPING AGENTS CAN BE EMPLOYED IN PHOTOGRAPHIC ELEMENTS AND/OR PROCESSING COMPOSITIONS. THEY CAN BE EMPLOYED IN COMBINATION WITH OTHER SILVER HALIDE DEVELOPING AGENTS AND ADDENDA EMPLOYED IN PHOTOGRAPHIC ELEMENTS AND/OR PROCESSING COMPOSITIONS. THEY ARE SUITABLE, FOR INSTANCE, IN ELEMENTS FOR DRY PROCESSING WITH HEAT, AND/OR PROCESSING SOLUTIONS AND/OR PHOTOGRAPHIC EMULSIONS.

I Rites atent a Patented Sept. 12, 1972 PHOTOGRAPHIC DEVELOPING PROCESS WITH AMINO HYDROXY CYCLOALKENONE Rolf S. Gabrielsen and Ismael A- Olivares, Rochester,

N.Y., assignors to Eastman Kodak Company, Rochester,N.Y. No Drawing. Filed Dec. 2, 1970, Ser. No. 94,567

' Int. Cl. G03c 5/30 US. C]. 96-66 HD 1 ABSTRACT on THE DISCLOSURE Photographic silver halide developing agents which are amino hydroxy cycloalkenone compounds having a five or six member cycloalkene nucleus provide increased-development activity, e.g. reduced development time, and

provide low-colored oxidation products without undesired sensitometn'c properties in developing a latent image 1n a l l Claims I 2,936,308 of Hodge, issued May 10, 1960 and, US. Pat. 2,691,589 of Henn et al. issued Oct. 12, 1954. They have also been employed in photographic elements for dry processing with heat as described in US. 3,301,678 of Humphlett et al., issued Jan. 31, 1967, and have also been employed in photographic elements as nucleating agents for direct positive photographic silver halide emulsions as described in U.S. Pat. 3,347,671 of Salminen issued Oct. 17, 1967.

photographic element. These developing agents can be employed in photographic elements and/ or processing compositions. They can be employed in combination with other silver halide developing agents and addenda employed 1n photographic elements and/or processing compositions.

They are suitable, for instance, in elementsfor dry processing with heat, and/or processing solutions and/or photographic emulsions.

BACKGROUND OF THE INVENTION I Field of the invention DESCRIPTION THE STATE OF THE ART It is well known to develop a latent image in a photographic silver halide element using. a silver halide developing agent. Developing agents for this purpose have included, for example, aminophenol, 3-pyrazolidone, ascorbic acid and polyhydroxybenzene developing agents. This isdescribed, for example, in The Theory of the Photo- .graphic Process by Mees and. James, 3rd edition, 1966,

It has been desirable to provide developing agents which are sutficiently active to provide desired sensitometric properties within the shortest development time and also result in colorless or low-colored oxidation products. Developing agents which provide colorless or low-colored oxidation products are especially desirable in photographic systems in which the oxidation products are not to be re movedfrom the system,-such as in systems in which usual washing with water is avoided.

. Certain reductone compounds have'been used as developing agents, as described, for example, in U.S. Pat.

halide developing In some cases, these may be combined with known developing agents such as hydroquinones, catechols, aminophenols, 3-pyrazolidones, ascorbic acid and its derivatives, and reductones in the practice of the invention. The developing agents can be in a silver halide emulsion and/or in another suitable location in the photographic element. The developing agents may be added from suitable solvents or in the form of dispersions as described in Yackel US. Pat. 2,592,368 issued Apr. 4, 1952 and Dunn et al., French Pat. 1,505,778 isued Nov. 6, 1967.

There has been a continuing need, however, to provide developing agents which provide desired developing activity, shortened development time, and result in colorless or low-colored oxidation products without loss of desired sensitometric properties.

SUMMARY OF THE INVENTION a photographic processing composition, element and/0r process employing an amino hydroxy cycloalkenone silver agent having a five or six member cyc.lo-

al-kenone nucleus.

DETAILED DESCRIPTION OF THE INVENTION 7 A wide range of described amino hydroxy cyclo alkenone silver halide developing agents can be employed according to the invention. Suitable amino hydroxy cycloalkenone silver halide developing agents include, for example, compounds of the formula:

wherein R, and R are each hydrogen, alkyl, especially alkyl containing 1 to 5 carbon atoms, e.g. methyl, ethyl, propyl, butyl or ,pentyl, or taken together are atoms completing a 5 or 6 member heterocyclic nucleus, as denoted by the broken line in Structure'I, e.g. morpholino, piper azino, pyn'olidino, piperidino, and the like; R and -R are each hydrogen, or alkyl containing 1 to 5 carbon atoms, e.g. methyl, ethyl, propyl, or butyl; n is 1 or 2.

The developing agents of the invention as described include their tautomeric-form and their salts, such as their alkali metal salts, e.g. sodium or potassium salts, sulfate or chloride salts.

Examples of suitable amino hydroxy cycloalkenones, as described are:

The described cycloalkenones employed as developing agents in accordance with the invention can be prepared for instance, by dehydrochlorination of compounds having the following structure:

in the presence of a suitable catalyst, such as triethylamine. These starting materials for the dehydrochlorination can be synthesized by the following sequence of reactions:

(CH3)2CHCH2CH;ON=0 F1101 R. H2)n 3%! R. (0H1).

HCllHzO R4 wherein R R and n are as described under Structure I. The preparation of 2 hydroxy-3-morpholino-2cyclohexenone is typical of the method of preparation of developing agents according to the invention. This preparation is described in an article by H. Simon, G. Heubach, W. Bitterlich and H. Gleinig in Chemische Berichte, vol. 98, pages 3692-3702 (1965). 'Equimolar amounts of morpholine, 3-chloro-1,2-cyclohexanedione and triethylamine are refluxed together for two days in anhyrous ethyl acetate under an atmosphere of nitrogen. After cooling the mixture, the crystals of triethylammonium chloride which form are separated by filtration. The filtrate is evaporated to dryness and the residue is purified, e.g. by recrystallization from absolute ether, yielding 2- hydroxy-3-morpholino-2-cyclohexenone. The following equation illustrates this preparation:

The described silver halide developing agents can be employed in the practice of the invention in a range of physical locations in a photographic system. They can be employed in one or more layers of a photographic element and/or in a processing composition if desired. The optimum location will depend upon the desired image, processing conditions and the like. For example, the aminohydroxy cycloalkenone silver halide developing agents can be employed in a processing composition, such as an aqueous alkaline developer solution or they can be incorporated into one or more layers of a photographic element, such as a photographic silver halide emulsion layer, a layer between the support and a silver halide emulsion layer, and/or an overcoat layer.

Accordingly, one embodiment of the invention is a photographic processing composition, especially a silver halide developer, comprising an alkaline development activator and the silver halide developing agent as described. This is typically an aqueous alkaline solution.

Various development activators can be employed in the practice of the invention. These include any of those which provide the desired activation of the described developing agent. These include, for instance, alkaline development activators, such as inorganic alkalies including, for example, sodium hydroxide, potassium hydroxide, and lithium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal phosphates sucn as trisodium phosphate, and organic alkaline development activators such as quaternary ammonium bases and salts, e.g. amino alkanols and similar alkaline materials and/or alkali releasing materials. Sufficient development activator is employed to provide desired activation. This is typically sufiicient to provide a pH of at least about 9.5, e.g. about 9.5 to about 14. The described development activators can be applied to the described photographic element in any suitable manner including, for example, dipping, spraying and/or suitable surface application such as with rollers or with other mechanical means.

A range of concentrations of the described developing agent can be employed in a processing composition in the practice of the invention, depending on the desired image, the developing agent employed, processing conditions and the like. When employed in a processing composition, such as an aqueous solution, a concentration of about 0.1 mole to about 3.0 moles of developing agent is suitable per liter of processing composition.

Stabilizing the resulting developed image in the process of the invention can be carried out by contacting the described photographic element with a suitable stabilizing agent, typically in an aqueous solution. Nonaqueous solutions can be employed if desired, such as solutions containing ethylene glycol or ethanol. Such a stabilizer solution can be applied in any suitable manner such as by dipping, spraying and/ or suitable surface application such as with rollers or with mechanical means.

A wide range of stabilizing agents commonly employed in photographic processing can be employed in the practice of the invention. Typical stabilizing agents employed in processing of photographic elements include, for example, ammonium thiocyanate, alkali metal thiocyanates, such as sodium thiocyanate and/or potassium thiocyanate, alkali metal thiosulfates such as sodium thiosulfate and potassium thiosulfate. Mixtures of stabilizing agents, such as a mixture of a thiocyanate stabilizing agent and a thiosulfate stabilizing agent can be employed.

Solutions containing a stabilizing agent employed in the practice of the invention can contain other materials, especially those known to provide beneficial results in stabilizer solutions. For instance, they can contain toning agents such as mercaptoazoles, particularly 3-mercaptotriazoles which further stabilize the image, e.g. against bleaching. Suitable mercaptoazoles which can be used for this purpose include mercaptoxazoles, mercaptothiazoles, selenazoles, mercaptotetrazoles, and the like. The aqueous solution of stabilizing agent can contain metal salts, e.g. water-soluble aluminum and/or chromium salts, such as aluminum sulfate, potassium aluminum sulphate, aluminum chloride, chrome alum, and the like.

The time for processing a photographic element in the practice of the invention, that is developing a desired image, can vary over a wide range, typically between about one second and several minutes, depending on the desired image, processing conditions and the like.

The conditions for processing can vary over wide ranges. Usually ambient pressures and temperatures of about 20 C. to about 30 C. are suitable but higher temperatures can be employed if desired, such as temperatures up to about 90 C. In the case of processing with heat, however, temperatures of about 80 C. to about 250 C. are suitable.

The developing agents employed in the practice of the invention can be employed in combination with any silver halide developing agent. The developing agents employed in the practice of the invention can be employed in such combination as auxiliary developing agents or as the main component of the developing combination. Suitable silver halide developing agents which can be employed in combination with the described developing agents include, for example, polyhydroxybenzenes such as hydroquinone developing agents, e.g. hydroquinone, alkyl-substituted hydroquinones as exemplified by tertiary butyl hydroquinone, methyl hydroquinone and 2,5-dimethyl hydroquinone; catechols and pyrogallol; chloro-substituted hydroquinones such as chloro hydroquinone or dichloro hydroquinone; alkoxy-substituted hydroquinones such as methoxy hydroquinone or ethoxy hydroquinone; amino phenol developing agents, such as 2,4-diamino phenols and methylamino phenols; ascorbic acid developing acids such as ascorbic acid ketals, and ascorbic acid derivatives such as those described in U.S. Pat. 3,337,342 of Green issued Aug. 22, 1967; hydroxylamine developing agents such as N,N-di(2-ethoxyethyl) hydroxylamine; 3-pyrazolidone developing agents such as 1-phenyl-3-pyrazolidone and 4 methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone, including those described in British 930,572 published July 3, 1963; and acyl derivatives of para-amino phenol such as described in British 1,045,303 published Oct. 12, 1966; hydroxy tetronic acid and hydroxy tetronimide developing agents; and cinnamic acid developing agents or lactone developing agent precursors described in Belgian Pat. 739,706; and the like.

The silver halide emulsions used with this invention can comprise silver chloride, silver bromide, silver bromoiodide, silver chlorobromoiodide or mixtures thereof. The emulsions may be coarse or fine grain and can be prepared by any of the well-known procedures, e.g. single jet emulsions, double jet emulsions, such as Lippmann emulsions, ammoniacal emulsions, thiocyanate or thioether ripened emulsions such as those described in Nietz et al. U.S. Pat. 2,222,264 issued Nov. 4, 1940; Illingsworth U.S. Pat. 3,320,069 issued May 15, 1967; and McBride U.S. Pat. 3,271,157 issued Sept. 6, 1966. Surface image emulsions may be used or internal image emulsions such as those described in Davey et a1. U.S. Pat. 2,592,250 issued Apr. 8, 1952; Porter et al. U.S. Pat. 3,206,313 issued Sept. 14, 19-65; Berriman U.S. Pat. 3,367,778 issued Feb. 2, 1968 and Bacon et a1. U.S. Pat. 3,447,927 issued June 3, 1969. If desired, mixtures of surface and internal image emulsions may be used as described in Luckey et al. U.S. Pat. 2,996,382 issued Apr. 15, 1961. Negative type emulsions may be used or direct positive emulsions such as those described in Leermakers U.S. Pat. 2,184,013 issued Dec. 19, 1939; Kendall et al. U.S. Pat. 2,541,472 issued Feb. 13, 1951; Berriman U.S. Pat. 3,367,778 issued Feb. 6, 1968; Schouwenaars British Pat. 723,019; Illingsworth et a1. French Pat. 1,520,821; Ives U.S. Pat. 2,563,785 issued Aug. 7, 1951; Knott et al. U.S. Pat. 2,456,953 issued Dec.

6 21, 1968 and Land U.S. Pat. 2,861,885 issued Nov. 25, 8. The emulsions may be regular grain emulsions such as the type described in Klein and Moisar, J. Phot. Sci., vol. 12, No. 5, Sept./Oct., 1964, pp. 242-251.

The silver halide emulsions used with this invention may be unwashed or washed to remove soluble salts. In the latter case the soluble salts may be removed by chillsetting and leaching or the emulsion may be coagulation washed, e.g. by the procedures described in Hewitson et al. U.S. Pat. 2,618,556 issued Nov. 18, 1952; Yutzy et al. U.S. Pat. 2,614,928 issued Oct. 21, 1952; Yackel U.S. Pat. 2,565,418 issued Aug. 21, 1951; Hart et al. U.S. Pat. 3,241,969 issued Mar. 22, 1966 and Waller et al. U.S. Pat. 2,489, 341 issued Nov. 29, 1949.

The emulsions used with this invention may be sensitized with chemical sensitizers, such as with reducing agents; sulfur, selenium or tellurium compounds; gold, platinum or palladium compounds; or combinations of these. Suitable procedures are described in Sheppard et al. U.S. Pat. 1,623,499 issued Apr. 5, 1927; Waller et al. U.S. Pat. 2,399,083 issued Apr. 23, 1946; McVeigh U.S. Pat. 3,297,447 issued Jan. 10, 1967; and Dunn U.S. Pat. 3,297,446 issued Jan. 10, 1967.

The silver halide emulsions used with this invention may contain speed increasing compounds such as polyalkylene glycols, cationic surface active agents and thioethers or combinations of these as described in Piper U.S. Pat. 2,886,437 issued May 12, 1959; Dann et al. U.S. Pat. 3,046,134 issued July 24, 1962; Carroll et al. U.S. Pat. 2,944,900 issued July 12, 1960 and Goife U.S. Pat. 3,294,540 issued Dec. 27, 1966.

The silver halide emulsions used in the practice of this invention can be protected against the production of fog and can be stabilized against loss of sensitivity during keeping. Suitable antifoggants and stabilizers each used alone or in combination include thiazolium salts described in Brooker et al. U.S. Pat. 2,131,038 issued Sept. 27, 1938 and Allen et al. U.S. Pat. 2,694,716 issued Nov. 16, 1954; the azaindenes described in Piper U.S. Pat. 2,886,437 issued May 12, 1959 and Heimbach et al. U.S. Pat. 2,444,605 issued July 6, 1948; the mercury salts as described in Allen et al. U.S. Pat. 2,728,663 issued Dec. 27, 1955; the urazoles described in Anderson et al. U.S. Pat. 3,287,135 issued Nov. 22, 1966; the sulfocatechols described in Kennard et al. U.S. Pat. 3,236,652 issued Feb. 22, 1966; the oximes described in Carroll et al. British Pat. 623,448; nitron; nitroindazoles; the mercaptotetrazoles described in Kendall et al. U.S. Pat. 2,403,927 issued July 16, 1946; Kennard et al. U.S. Pat. 3,266,897 issued Aug. 16, 1966 and Luckey et al. U.S. Pat. 3,397,987 issued Aug. 20, 168; the polyvalent metal salts described in Jones U.S. Pat. 2,839,405 issued June 17, 1958; the thiuronium salts described in Herz et al. U.S. Pat. 3,220,839 issued No. 30, 1965; the palladium, platinum and gold salts described in Trivelli et al. U.S. Pat. 2,566,263 issued Aug. 28, 1951 and Yutzy et al. U.S. Pat. 2,597,915 issued May 27, 1952.

The photographic and other hardenable layers used in the practice of this invention can be hardened by various organic or inorganic hardeners, alone or in combination, such as the aldehydes, and blocked aldehydes, ketones, carboxylic and carbonic acid derivatives, sulfonate esters, sulfonyl halides and vinyl sulfonyl ethers, active halogen compounds, epoxy compounds, aziridines, active olefins, isocyanates, carbodiimides, mixed function hardeners and polymeric hardeners such as oxidized polysaccharides like dialdehyde starch and oxyguargum and the like.

The photographic emulsions and elements described in the practice of this invention can contain various colloids alone or in combination as vehicles, binding agents and various layers. Suitable hydrophilic materials include both naturally-occurring substances such as proteins, for example, gelatin derivatives, cellulose derivatives, polysuccharides such as dextran, gum arabic and the like; and synthetic polymeric substances such as'water soluble polyvinyl compounds like poly(vinylpyrrolidone), acrylamide polymers and the like.

The described photographic emulsion layers and other layers of a photographic element employed in the practice of this invention can also contain alone or in combination with hydrophilic, water permeable colloids, other synthetic polymeric compounds such as dispersed vinyl compounds such as in latex form and particularly those which increase the dimensional stability of the photographic materials. Suitable synthetic polymers include those described, for example, in Nottorf U.S. Pat. 3,142,568, issued July 28, 1964; White U.S. Pat. 3,193,386, issued July 6, 1965; Houck et al. U.S. Pat. 3,062,674, issued Nov. 6, 1962; Houck et al. U.S. Pat. 3,220,844, issued Nov. 30, 1965; Ream et al. U.S. Pat. 3,287,289, issued Nov. 22, 1966; and Dykstra U.S. Pat. 3,411,911, issued Nov. 19, 1968; particularly effective are those water-insoluble polymers of alkyl acrylates and methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates, those which have crosslinking sites which facilitiate hardening or curing, those having recurring sulfobetaine units as described in Dykstra Canadian Pat. 774,054.

The photographic elements used with this invention may contain antistatic or conducting layers, such layers may comprise soluble salts, e.g. chlorides, nitrates, etc., evaporated metal layers, ionic polymers such as those described in Minsk U.S. Pat. 2,861,056 issued Nov. 18, 1958 and Sterman et al. U.S. Pat. 3,206,312 issued Sept. 14, 1965 or insoluble inorganic salts such as those described in Trevoy U.S. Pat. 3,428,451 issued Feb. 18, 1969.

The photographic layers and other layers of a photographic element employed and described herein can be coated on a wide variety of supports. Typical supports include cellulose nitrate film, cellulose ester film, poly- (vinyl acetal) film, polystyrene film, poly(ethylene terephthalate) film, polycarbonate film and related films or resinous materials, as well as glass, paper, metal and the like. Typically, a flexible support is employed, especially a paper support, which can be partially acetylated or coated with baryta and/or an alpha-olefin polymer, particularly a polymer of an alpha-olefin containing 2 to carbon atoms such as polyethylene, polypropylene, ethylenebutene copolymers and the like.

The photographic layers employed in the practice of this invention can contain plasticizers and lubricants such as polyalcohols, e.g. glycerin and diols of the type described in Timmons et al. U.S. Pat. 2,960,404 issued Nov. 1, 1966; fatty acids or esters such as those described in Robijns U.S. Pat. 2,588,765 issued Mar. 11, 1952 and Duane U.S. Pat. 3,121,060 issued Feb. 11, 1964 and silicone resins such as those described in DuPont British Pat. 955,061.

The photographic layers employed in the practice of this invention may contain surfactants such as saponin; anionic compounds such as the alkyl aryl sulfonates described in Baldsiefen U.S. Pat. 2,600,831 issued June 17, 1962; amphoteric compounds such as those described in Ben-Ezra U.S. Pat. 3,133,816 issued June 19, 1964; and water soluble adducts of glycidol and an alkyl phenol such as those described in Olin Matheison British Pat. 1,022,878.

The photographic elements employed in the practice of this invention may contain matting agents such as starch, titanium dioxide, zinc oxide, silica, polymeric beads including beads of the type described in Jelley et al. U.S. Pat. 2,992,101 issued July 11, 1961 and Lynn U.S. Pat. 2,701,245 issued Feb. 1, 1955.

The photographic elements used in this invention may contain brightening agents including stilbenes, triazines, oxazoles and coumarin brightening agents. Water soluble brightening agents may be used such as those described in Albers et al. German Pat. 972,067 and McFall et al.

U.S. Pat. 2,933,390 issued Apr. 19, 1960 or dispersions of brighteners may be used such as those described in Jansen German Pat. 1,150,274, Oetiker et al. U.S. Pat. 3,406,070 issued Oct. 15, 1968 and Heidke French Pat. 1,530,244.

Spectral sensitizing dyes can be used conveniently to confer additional sensitivity to the light senstive silver halide emulsion of the multilayer photographic elements of the invention. For instance, additional spectral sensitization can be obtained by treating the emulsion with a solution of a sensitizing dye in an organic solvent or the dye may be added in the form of a dispersion as described in Owens et al. British Pat. 1,154,781. For optimum results, the dye may either be added to the emulsion as a final step or at some earlier stage.

sensitizing dyes useful in sensitizing such emulsions are described, for example, in Brooker et al. U.S. Pat. 2,526,632 issued Oct. 24, 1950; Sprague U.S. Pat. 2,503,- 776 issued Apr. 11, 1950; Brooker et al. U.S. Pat. 2,493,- 748 issued Jan. 10, 1950 and Taber et al. U.S. Pat. 3,384,486 issued May 21, 1968. Spectral sensitizers which can be used include the cyanines, merocyanines, complex (tri or tetranuclear) merocyanines, complex (tri or tetranuclear) cyanines, holopo lar cyanines, styryls, hemicyanines (e.g. enamine hemicyanines), oxonols and hemioxonols.

Dyes of the cyanine classes may contain such basic nuclei as the thiazolines, oxazolines, pyrrolines, pyridines, oxazoles, thiazoles, selenazoles and imidazoles. Such nuolei may contain alkyl, alkylene, hydroxyalkyl, sulfoalkyl, carboxyalkyl, aminoalkyl and enamine groups and may be fused to carbocyclic or heterocyclic ring systems either unsubstituted or substituted with halogen, phenyl, alkyl, haloalky l, cyano, or alkoxy groups. The dyes may be symmetrical or unsymmetrical and may contain alkyl, phenyl, enamine or heterocyclic substitutents on the methine or polymethine chain.

The merocyanine dyes may contain the basic nuclei mentioned above as well as acid nuclei such as thiohydantoins, rhodanines, oxazolidenediones, thiazolidenediones, barbituric acids, thiazolineones, and malononitrile. These acid nuclei may be substituted with alkyl, alkylene, phenyl, carboxyalkyl, sulfoalkyl, hydroxyalkyl, alkoxyalkyl, alkylamino groups, or heterocyclic nuclei. Combinations of these dyes may be used, if desired. In addition, supersensitizing addenda which do not absorb visible light may be included, for instance, ascorbic acid derivatives, azaindenes, cadmium salts, and organic sulfonic acids as described in McFall et al. U.S. Pat. 2,933,390 issued Apr. 19, 1960 and Jones et al. U.S. Pat. 2,937,089 issued May 17, 1960.

The various layers, including the photographic layers, employed in the practice of this invention can contain light absorbing materials and filter dyes such as those described in Sawdey U.S. Pat. 3,253,921 issued May 31, 1966; Gaspar U.S. Pat. 2,274,782 issued Mar. 3, 1942; Silberstein et al. U.S. Pat. 2,527,583 isued Oct. 31, 1950 and VanCampen U.S. Pat. 2,956,879 issued Oct. 18, 1960. If desired, the dyes can be mordanted, for example, as described in Jones et al. U.S. Pat. 3,282,699 issued Nov. 1, 1966.

The sensitizing dyes and other addenda used in the practice of this invention may be added from water solutions or suitable organic solvent solutions may be used. The compounds can be added using various procedures including those described in Collins et al. U.S. Pat. 2,912,343 issued Nov. 10, 1959; McCrossen et a]. U.S. Pat. 3,342,605 isued Sept. 19, 1967; Audran U.S. Pat. 2,996,287 isued Aug. 15, 1961 and Johnson et al. U.S. Pat. 3,425,835 issued Feb. 4, 1969.

The photographic layers used in the practice of this invention may be coated by various coating procedures including dip coating, air knife coating, curtain coating, or extrusion coating using hoppers of the type described in Beguin U.S. Pat. 2,681,294 issued June 15, 1954. If

desired, two or more layers may be coated simultaneously by the procedures described in Russell U.S. Pat. 2,761,791 issued Sept. 4, 1956 land Wynn British Pat. 837,095. This invention also can be used for silver halide layers coated by vacuum evaporation as described in British Pat. 968,453 and Lu Valle et a1. U.S. Pat. 3,219,451 issued Nov. 23, 1965.

This invention may be used with elements designed for colloid transfer processes such as described in Yackel et al. U.S. Pat. 2,716,059 issued Aug. 23, 1955; silver salt diffusion transfer processes such as described in Rott U.S. Pat. 2,352,014 issued June 20, 1949; Land U.S. P'at. 2,543,181 isued Feb. 27, 1951; Yaokel et a1. U.S. Pat. 3,020,155 issued Feb. 6, 1962 and Land U.S. Pat. 2,861,- 885 issued Nov. 25, 1958; color image transfer processes such as described in Rogers U.S. Pats. 3,087,817 issued Apr. 30, 1963; 3,185,567 issued May 25, 1965 and 2,983,- 606 issued May 9, 1961; Weyerts et al. U.S. Pat. 3,253,- 915 issued May 31, 1966; Whitmore et al. U.S. Pats. 3,227,550 issued January 4, 1966; 3,227,551 issued January 4, 1966 and 3,227,552 issued January 4, 1966 and Land U.S. Patents 3,415,644 issued December 10, 1968, 3,415,645 issued December 10, 1968; 3,415,646 issued December 10, 1968 and imbibition transfer processes as described in .Minsk U.S. Patent 2,882,156 issued Apr. 14, 1959.

This invention may be used in elements designed for recording print out images as described in Fallesen U.S. Pat. 2,369,449 or Bacon et al. U.S. Pat. 3,447,927 issued June 3, 1969; direct print images as described in Hunt U.S. Patent 3,033,682 issued May 8, 1962 and McBride U.S. P'at. 3,287,137 issued Nov. 22, 1966; elements designed for procesing by heat as described in Sorensen et al. U.S. Pat. 3,152,904 issued Oct. 13, 1964; Morgan et al. U.S. Pat. 3,457,075 issued July 22, 1964; Stewart et al. U.S. Pat. 3,312,550 issued Apr. 4, 1967 and Colt U.S. Pat. 3,418,122 issued Dec. 24, 1968. This invention may be used in elements designed for physical development such as those described in Agfa British Pat. 920,277 and Gilman et al. British Pat. 1,131,- 238.

This invention may be used with elements designed for color photography, for example, elements containing color-forming couplers such as those described in Frohlich et al. U.S. Pat. 2,376,679 issued May 22, 1945; Jelley et al. U.S. Pat. 2,322,027 issued June 15, 1943; Fierke et al. U.S. Pat. 2,801,171 issued July 31, 1957; Godowsky U.S. Pat. 2,698,794 issued Jan. 4, 1966; Barr et al. U.S. Pat. 3,227,554 issued Jan. 4, 1966 and Graham et al. U.S. Pat. 3,046,129 issued July 24, 1962; or elements to be developed in solutions containing color-forming couplers such as those described in Mannes et al. U.S. Pat. 2,252,718 issued Aug. 19, 1941; Carroll et al. U.S. Pat. 2,592,243 issued Apr. 8, 1952 and Schwan et al. U.S. Pat. 2,950,970 issued Aug. 30, 1960; and in false-sensi tized color materials such as those described in Hanson U.S. Pat. 2,763,549 issued Sept. 18, 1956.

Photographic elements prepared according to this invention can be processed by various methods including processing in alkaline solutions containing the described developing agents. The solutions can also contain other developing agents, such as hydroquinones, catechols, aminophenols, 3-pyrazolidones, phenylenediamines, ascorbic acid derivatives, hydroxylamines, hydrazines, reductones and the like; web processing such as described in Tregillus et al. U.S. Pat. 3,179,517 issued Apr. 20, 1965; stabilization processing as described in Russell et a1. Stabilization Processing of Films and Papers, PSA Journal, vol. 16B, August 1950; monobath processing as described in Levy Combined Development and Fixation of Photographic Images with Monobaths, Phot. Sci. and Eng, vol. 2, No. 3, October 1958, and Barnes et al. U.S. Pat. 3,392,019 issued July 9, 1968. If desired, the photographic elements of this invention can be processed in hardening developers such as those described in Allen et al. U.S. Pat. 3,232,761

10 issued Feb. 1, 1966; in roller transport processors such as those described in Russell et al. U.S. Pat. 3,025,779 issued Mar. 2, 1962; or by surface application processing as described in Example 3 of Kitze U.S. Pat. 3,418,132 issued Dec. 24, 1968.

Another embodiment of the invention is a photographic composition comprising a photographic silver halide and an amino hydroxy cycloalkenone silver halide developing agent, as described. This composition is typically a photographic silver halide emulsion.

A further embodiment is a photographic element comprising a support, photographic silver halide and an amino hydroxy cycloalkenone silver halide developing agent, as described.

The concentration of developing agent in such compositions and elements can vary depending upon the desired image, particular developing agent employed, processing conditions and the like. A concentration of about 0.1 mole to about 4.0 moles of developing agent per mole of silver halide present is suitable.

A further embodiment of the invention is: in a photographic process comprising developing a latent image in an exposed photographic silver salt in the presence of a silver halide developing agent, the improvement comprising employing an amino hydroxy cycloalkenone silver developing agent as described.

The developing agents employed in the practice of the invention can be employed in an element containing development nuclei or silver precipitating nuclei, such as an image receiver. As described, they can also be employed in photographic elements and/or processing compositions designed for use with an image receiver. Development nuclei or silver precipitating agents which can be employed in diffusion transfer systems, as described, can be physical development nuclei or chemical precipitants including, for example: (a) heavy metals in colloidal form and salts of these metals, (b) salts of amines which form silver salts and/or (0) nondiifusing polymeric materials with functional groups capable of combining with silver amines.

Suitable development nuclei and/or silver image precipitating agents within the described classes include metal sulfides, selenides, polysulfides, polyselenides, thiourea and its derivatives, stannous halides, sulfur, gold, platinum, palladium, and mercury, colloidal sulfur, aminoguanidine sulfate, aminoguanidine carbonate, arsenous oxide, sodium stannite, hydrazines, xanthates and similar agents disclosed, for example, in U.S. Pat. 3,020,155 of Yackel et al. issued Feb. 6, 1962. A nonditfusing polymeric silver precipitant or development nuclei, such as poly- (vinylmercaptoacetate) can also be employed.

A wide range of concentrations of development nuclei or silver precipitating agents can be employed. A concentration of the development nuclei or silver precipitant in the image receiving layer must be at least sufficient to insure the development of a positive image and sufficient removal of undeveloped silver salt from the light-sensitive layer to be processed. Usually the concentration of the developing agents, as described, is about 320 milligrams per square foot of the layer containing the precipitants or development nuclei.

The developing agents, as described, can be employed in photographic elements for processing with heat. For example, an embodiment of the invention is a process of developing a latent image in an exposed photographic element comprising a support, photographic silver halide and a developing agent, as described, comprising heating the element to about C. to about 250 C. The time suitable for developing an image is typically about 1 to about 60 seconds, depending upon the components of the element, desired image, processing temperature and the like.

i The process employing heat is typically a process of developing and stabilizing a latent image in an exposed photographic element comprising a support, (a) photographic silver halide, (b) an amino hydroxy cycloalkenone silver halide developing agent, as described, and (c) an image stabilizer precursor comprising heating the element to about 80 C. to about 250 C. The stabilizer precursor may be a sulfur containing compound which upon heating forms acompound that combines with unexposed silver halide to form a silver mercaptide which is more stable to light than the silver halide. Suitable stabilizer precursors are isothiuronium compounds, as described in US. Pat. 3,301,678 of Humphlett et al., issued Jan. 31, 1967; Belgian Pat. 709,899; and Belgian Pat. 709,967. Other isothiuronium stabilizer precursors which are suitable are bis(isothiuronium) compounds such as 1,8-(3,6-dioxaoctane)bis(isothiuronium) dichloride and/ or 1,9-(3,6- dioxaoctane) bis (isothiuronium bis (trifluoroacetate) A range of concentration of stabilizer precursor can be employed depending upon processing conditions, particular components of the element, and the like. A concentration of stabilizer precursor of about 0.1 mole to about 4.0 mole of stabilizer precursor per mole of silver halide in the element is sufiicient.

Another embodiment of the invention is a photosensitive and thermosensitive element comprising a support, (a) an oxidation-reduction image-forming combination comprising (1) a reducing agent, which comprises an aminohydroxy cycloalkenone silver halide developing agent as described, with (2) an oxidizing agent which comprises a heavy metal salt of an organic carboxylic acid, (b) a catalyst for said image-forming combination, e.g. photosensitive silver halide and, preferably, (c) an activator-toning agent such as phalazinone.

Another embodiment is a photosensitive and thermosensitive composition comprising (a) the described oxidation-reduction image-forming combination, (b) a catalyst for said image-forming combination, as described, and, preferably, an activator-toning agent.

The described photosensitive and thermosensitive element or composition contains a catalyst for the imageforming combination, especially a photosensitive silver salt. A typical concentration range of photosensitive silver salt is from about 0.005 to about 0.50 mole of silver salt per mole of oxidizing agent, e.g., per mole of silver behenate. A preferred catalyst is photosensitive silver halide, e.g., silver chloride, silver bromide, silver bromoiodide, silver chlorobromoiodide, or mixtures thereof.

Other suitable organic reducing agents which can be employed in the described oxidation-reduction imageforming combination include, for example, the described silver halide developing agent and substituted phenols or naphthols. Bis-fl-naphthols can be employed in the described combination such as:

2,2-dihydroxyl l '-binaphthyl, 6,6'-dibromo-2,2'-dihydroxy-1,1-binaphthyl, 6,6-dinitro-2,2-dihydroxy-l,1-binaphthyl, or Bis- (2-hydroxyl-naphthyl) methane.

The described reducing agents are suitable in a range of concentration in the described photosensitive and thermosensitive element or composition; however, they are especially suitable, at a concentration from about 0.10 to about 0.75 mole of reducing agent per mole of oxidizing agent, e.g., per mole of silver behenate.

The described photosensitive and thermosensitive elements and compositions comprise an oxidizing agent, especially a heavy metal salt of an organic acid. The heavy metal salts of the organic acids should be resistant to darkening under illumination to prevent undesired deterioration of a developed image. An especially suitable class of heavy metal salts of organic acids is represented by the water insoluble silver salts of long-chain fatty acids which are stable to light. Compounds which are suitable silver salts include behenate, silver stearate, silver oleate, silver laurate, silver hydroxystearate, silver caprate, silver myristate and silver palmitate.

Other suitable carboxylic acid silver salt oxidizing agents, which are not silver salts of long-chain fatty acids include silver benzoate, silver 4'-n-octadecyloxydiphenyl- 4-carboxylate, silver o-amino benzoate, silver acetamidobenzoate, silver furoate, silver camphorate, silver pphenylbenzoate, silver phenylacetate, silver salicylate, silver butyrate, silver terephthalate, silver phthalate, silver acetate and silver acid phthalate.

Oxidizing agents which are not silver salts of a carboxylic acid can be employed, if desired, such as silver phthalazinone, silver benzotriazole and silver saccharin. Oxidizing agents which are not silver salts can be employed, if desired, such as zinc oxide, gold stearate, mercuric behenate, auric behenate and the like, but silver salts are preferred.

It is desirable to employ an activator-toning agent in the described photosensitive and thermosensitive elements and compositions to obtain a desired image. The described activator-toning agents are suitable in a range of concentration; however, they are especially suitable at a concentration of about 0.10 mole to about 1.05 moles of activator-toning agent per mole of oxidizing agent, e.g., per mole of silver behenate. Suitable activator-toning agents which can be employed include cyclic imide activator-toning agents such as: phthalimide, N-hydroxyphthalimide, N- potassium phthalimide, N-silver phthalimide, N-mercury phthalimide, succinimide, and/or N-hydroxysuccinimide. Other activator-toning agents can be employed in combination with or in place of the described cyclic imide activator-toning agents. Typically a heterocyclic organic toning agent containing at least two hetero atoms in the heterocyclic ring of which at least one is a nitrogen atom is employed. These are described, for example, in US. Pat. 3,080,254 of Grant issued Mar. 5, 1963. Suitable toners include, for example, phthalazinone, phthalic anhydride, 2-acetylphthalazinone and 2-phthalylphthalazinone. Other suitable toners are described, for example, in US. Pat. 3,446,648 of Workman issued May 27, 1969.

A divalent metal salt which has the property of amplifying the developed image can be employed in the described photosensitive and thermosensitive elements and compositions to cause an increase in maximum image density. A suitable divalent metal salt image amplifier is zinc acetate, cadmium acetate or cupric acetate. The described image-amplifying compounds are suitable in a range of concentration of about 0.005 to about 0.20 mole of divalent metal salt image amplifier per mole of silver salt oxidizing agent.

It is desirable to employ an image stabilizer precursor in the described photosensitive and thermosensitive elements or compositions. These can be employed in the practice of the invention to reduce the amount of postprocessing print-out due to room light exposure and to reduce the background stain. Suitable stabilizer precursors include azole thioethers and blocked azole thione stabilizer precursors, e.g., 5 acetyl 4 methyl-2-(3-oxobutylthio) thiazole, 4 furoyl 3 methylthio 1, 2,4-thiadiazole- 5 thione, 5 acetyl 4 methyl 3 (3-oxobutyl)- thiazoline 2 thione and 2,6 di-tert-butyl-4-(l-phenyl- 5 tetrazolyl)thiophenol. The described stabilizer precursors are suitable in a range of concentration, e.g., at a concentration from about 0.002 mole to about 0.10 mole of stabilizer precursor per mole of oxidizing agent, e.g., per mole of silver behenate in an element or composition as described.

A range of colorless onium halides can be employed in the described photosensitive and thermosensitive elements or compositions to provide an additional increase in photosensitivity, i.e., speed, and in some cases to obtain a reduction in background density. A suitable speed-increasing onium halide compound is a quaternary ammonium halide, quaternary phosphonium halide and/or a tertiary sulfonium halide, e.g., l-phenethyl-Z-picolinium bromide, tetraethylphosphonium bromide or trimethyl- 13 sulfonium iodide. An especially suitable onium halide is trimethylp-henylammonium bromide which is typically employed at a concentration of about 0.10 mole to about 0.05 mole per mole of catalyst, e.g., per mole of photosensitive silver halide.

Photosensitive and thermosensitive elements and compositions, asdescribed, can contain various colloids alone or in combination as vehicles, binding agents and in various layers. These materials can be hydrophobic, but hydrophilic materials can also be employed. Preferred high molecular weight materials and resins include polyvinyl butyral, cellulose acetate butyrate, polymethyl methacrylate, poly(vinyl pyrrolidone), ethyl cellulose, polystyrene, polyvinyl chloride, chlorinated rubber, polyisobutylene, butadiene-styrene copolymers, vinyl chloridevinyl acetate copolymers, copolymers of vinyl acetate, vinyl chloride and maleic acid and polyvinyl alcohol.

If desired, the photosensitive silver halide can be prepared in situ, in the photosensitive and thermosensitive element or composition which can be employed in the practice of the invention. Such a method is described, for example, in US. Pat. 3,457,075 of Morgan et al. issued July 22, 1969.

The photosensitive silver halide can be prepared on the oxidizing agent, such as silver behenate or silver stearate, or other organic silver salt, prior to application of the silver halide on the support employed. This is also described in US. Pat. 3,457,075 of Morgan et al. issued July 22, 1969.

Stability to print out from light exposure is increased by employing highly purified materials; for example, freedom from halides and sulfides increase stability to light exposure. The use of highly purified silver behenate can, for example, reduce propensity to print out in background areas of an element prepared according to the invention.

An especially suitable photosensitive and thermosensitive element or composition, as described, comprises:

(a) polyvinylbutyral binder,

(b) an oxidizing agent comprising silver behenate,

(c) a reducing agent, as described,

(c) a reducing agent, as described,

(d) photosensitive silver halide,

(e) phthalimide activator-toning agent (f) zinc acetate image amplifier,

(g) l-phenethyl-Z-picolinium bromide or trimethylphenylammonium bromide,

(h) -acetyl-4-methyl-2-(3-oxobutylthio)thiazole as a stabilizer precursor, and

(i) a blue speed-increasing sensitizing dye comprising 3 carboxymethyl 5 [(3 methyl 2(3H)-thiazolinylidene]-isopropylidene]rhodanine, 3 ethyl 5- [(3 ethyl 2(3H)-benzothiazolylidene)-isopropylidene] ,2 thio 2,4- oxazolidenedione or 1 carboxymethyl 5 [(3 ethyl 2(3H)-benzoxazolylidene)- ethylidene -3 -phenyl-2-thiohydantoin.

After exposure of the described photosensitive and thermosensitive element, the resulting latent image is developed merely byheating the element, e.g. to about 80 C. to about 250 C. By increasing or decreasing the length of time of heating, a higher or lower temperature within the described range can be employed. A developed image is typically produced within a few seconds such as about 0.5 second to about 60 seconds.

Any suitable means can be used for providing the desired processing temperature range. The heating means can be a simple hot plate, iron, roller or the like.

In some cases, if desired, an element can be prepared wherein the described silver halide can be in one layer and other components in other layers.

Other addenda known to be useful in photosensitive and thermosensitive elements, such as described in British Pat. 1,161,777 published Aug. 20, 1969, US. Pat. 3,152,904 of Sorensenand Shepard issued Oct. 13, 1964 and UJSfPat. 3,457,075 of Morgan and Shely pattened 14 July 22, 1969 can be employed in the practice of the invention. r

The following examples are included for a further understanding of the invention.

EXAMPLES 1-6 Mole Developing agent 0.02 Sodium sulfite 0.2 Sodium carbonate 0.2

Water to 1.0 liter.

Various developing agents are used in the developer composition. In Developer A, hydroquinone is employed; in Developer B, piperidino hexose reductone described herein as PHR is employed; in Developer C, 2-hydroxy- 3-piperidino-2-cyclohexenone, described herein as HPCH is employed. In Developer D, 2-hydroxy-3-morpholino-2- cyclohexenone, described herein as HMOH is employed. In Developer E, 2-hydroxy-3-piperidino-2-cyclopentenone described herein as HPCP is employed. In Developer F, 3 dimethylamino 2 hydroxy 2 cyclohexenone described herein as DHCH is used. The activity of each of the developers is measured in terms of the time required to obtain a density of 2.0 on the 4th step of the sensitometric strip. These times are entered in Table I. It will be seen that the developing agents of the invention provide .a maximum density of 2.0 in surprisingly less time than the developing agents of Examples 1 and 2.

TABLE I.ACTIVITY AT pH 10.0

Time of i develop- Example No Developer Developing agent ment, min.

- Hydroquinoneu ufln 12.5

. PHR

1 Prior art: 2 Invention.-

EXAMPLES 7-12 TABLE IL-ACTIVIIY AT pH 11.5

Time of develop- Example No. Developer Developing agent merit, min.

7 G 1 3. 6 8 H l 3. 0 9 I 2 1. 7 1.5 l. 2 2. 2

l Prior art.

2 Invention.

" EXAMPLES 1 3-17 These examples illustrate employing a combination of developing agents according to the invention.

. The procedure set out in Examples 8-12 are repeated except that 0.02 mole of hydroquinone is added to each developer. The results which are obtained are set out in Table IH. It is observed that a combination of hydroquinone with DHCH or with HMOH provides sur- 15 prisingly less development time to provide a maximum density of 2.0 as described in Example 1.

EXAMPLES 18-24 Twenty milligram samples of the developing agents as set out in Table IV are placed in 10 ml. beakers and 1 ml. of (a) aqueous 4% by weight sodium hydroxide solution, or (b) aqueus 4% by weight sodium hydroxide plus 6% by weight sodium sulfite solution are added. The resulting solution is stirred to dissolve the developing agent. After five minutes the solution is absorbed into a 1 /2 x Z-inch piece of chromatographic paper. This is placed in a museum jar over water for 24 hours at room temperature. The strips are then dried and the densities read to neutral transmitted light on a densitometer (Kodak Model 31A Densitometer), in comparison with the untreated paper base. The density of the untreated paper is substracted to give the net stain density as set out in Table IV.

The results set out in Table IV demonstrate that developing agents of the invention provide surprisingly lower net stain density. i

TABLE IV Net stain density (b) With r V V sodium Example No. Developer Developing agent (a) Alone sulfite Hydroquinone. 1. 90 0. 34 2,4-diamino- 3. 82 2. 75

phenol. PHR 0. 12 0. 06 HPGH 0. 05 0. 02 HMOH 0.06 0.04 HPCP 13 0.06 DHCH 0 11 0. 06

1 Prior art. Invention.

EXAMPLE 25 This illustrates use of a material for diffusion transfer according to the invention.

A processing composition is prepared by mixing the following components:

G. Water 850 ml. Potassium sulfite2H O 50 Sodium thiosulfate-I-I O 40 Potassium iodide 1.6 Potassium hydroxide 16.7 Sodium hydroxide 17.5 DHCH Hydroxyethyl cellulose 32 Natrosol 250H, sold by Hercules Powder Co., U.S.A.)

A photographic element which is a paper support having a layer of coarse grain silver iodobromide gelatino emulsion is exposed sensitometrically.

An image receiver is prepared by coating a. water resistant paper support with palladium development nuclei dispersed in a polymeric binder.

The processing composition, as described, is then squeezed between the photographic element and the image receiver by running between two rollers. After 30 seconds, the so-called sandwich is peeled apart and the resulting image on the image receiver is observed.

Employing this procedure and the described photographic element, processing composition and image re- 16 ceiver, a good positive image is produced on the receiver having a maximum density of 1.42.

EXAMPLE 26 This illustrates use of a developing agent of the invention in a photographic emulsion.

0.169 gram of 3 dimethylamino-2-hydroxy-2-cyclohexenone (DHCH) (0.0012 mole) is incorporated in 16 milliliters of an emulsion containing 0.0004 mole silver chloride and about 8.5 percent by weight of pigskin gelatin. The pH of the gelatin is adjusted to 4.5 with sulfuric acid. This emulsion is hand-coated on a white-pigmented film support at an estimated silver coverage of about 35 mg. per ft. and air-dried.

EXAMPLE 27 A piece of photographic film prepared as described in Example 26 is exposed through a test object to tungsten light and the resulting latent image is developed with no visible fog by immersion for eight seconds at about 20 C. in an aqueous activator solution containing 25.0 grams sodium carbonate monohydrate and 25.0 grams anhydrous sodium sulfite per liter, with acetic acid added to pH 10.0. Activation is followed by fixing and washing. The maximum density is at least 2.0.

EXAMPLE 28 A piece of photographic film prepared as described in Example 26 is exposed through a test object to tungsten light and the resulting latent image is developed with no visible fog by immersion for 200 seconds in an aqueous borax solution containing suificient borax to provide a pH of 9.18. Activation is followed by fixing and Washin Similar results to those of Example 27 are obtained.

EXAMPLE 29 A piece of photographic film prepared as described in Example 26 is exposed through a test object to tungsten light and the resulting latent image is developed by suspending the film in a closed container over an aqueous solution containing 28% by weight of ammonium hydroxide for 60 seconds. Activation is followed by fixing and washing. Similar results to those of Example 27 are obtained.

EXAMPLE 30 This illustrates use of a developing agent of the invention in a photographic element for processing with heat.

0.169 gram of 3-dimethylamino-Z-hydroxy-Z-cyclohexenone (DHCH) (0.0012 mole) is incorporated in 8.0 milliliters of an emulsion containing 0.0004 mole silver chloride, 0.017 gram (0.0005 mole) of 1,8-(3,6-dioxaoctane)bis(isothiuronium) dichloride, and 0.173 gram (0.00035 mole) of 1,9 (3,6 dioxaoctane)bis(isothiuronium) bis-(trifiuoroacetate), and about 10 percent by weight pigskin gelatin. This emulsion is hand coated on a polyethylene coated paper support at an estimated silver coverage of about 70 mg. per ft. and air-dried.

A piece of the resulting photographic paper is sensitometrically exposed and then contacted with a metal plate at a temperature of C. for 20 seconds, producing a dense brown-black image on a light cream-colored background. The paper does not darken on further exposure to strong light.

EXAMPLE 31 colored background. The background does not darken further upon exposure to room light.

EXAMPLE 32 This is a comparative example.

The procedure set out in Example 31 is repeated with the exception that hydroquinone is employed in place of the described developing agent of the invention. A very weak image is produced.

EXAMPLE 33 EXAMPLE 34 This illustrates development and stabilization of an image employing an aqueous alkaline activator.

0.169 gram of 3 dimethylamino 2 hydroxy-2-cyclohexenone (DHCH) (0.0012 mole) is incorporated in 8.0 milliliters of an emulsion containing 0.0004 mole of silver chloride, 0.017 gram (0.0005 mole) of 1,8-(3,6-dioxaoctane)-bis(isothiuronium) dichloride, and 0.173 gram (0.00035 mole) of 1,9-(dioxaoctane)bis(isothiuronium) bis-(trifluoroacetate), and about 10% by weight pigskin gelatin. The emulsion is hand coated on a polyethylene coated paper support at an estimated silver coverage of about 70 mg. per ft. and air-dried.

A piece of the resulting photographic paper is sensitometrically exposed to tungsten light and then immersed for 5 seconds at 22 C. in an aqueous alkaline activator containing 20 grams of sodium hydroxide per liter of water, then washed with water and dried.

A dense black image is produced. The processed element shows no print out on exposure to room light.

EXAMPLE 35 This further illustrates development and stabilization of an image employing an aqueous alkaline activator.

The following components are mixed:

U.S.A.) 1.0 ml. Water to 20.0 ml. pH adjusted to 5.25.

This provides a so-called processing composition. A photographic element is prepared by applying a gelatino silver chloroiodide emulsion at 32 milligrams per square foot of silver and 120 milligrams per square foot of gelatin on a paper support. A so-called processing layer is applied on the silver chloroiodide emulsion layer by coating the described processing composition on the emulsion layer at a wet thickness of 0.004 inch.

The resulting element is dried and then sensitometrical- 1y exposed. It is then immersed in an aqueous 3% by weight sodium hydroxide solution for four seconds. A developed and stabilized image results having a maximum density of 1.04 and a minimum density of 0.13.

EXAMPLES 36-37 A dispersion is prepared by mixing the following components:

The mixture is ball milled for 18 hours. Phthalazinone or phthalimide is then incorporated as an activator-toner in approximately /2 the weight of the silver behenate. 3- dimethylamino-2-hydroxy-2-cyclohexenone, DHCH, is incorporated in the composition from alcohol-acetone solution. The concentration is approximately A the weight of the silver behenate. The composition is coated on a paper support at a wet thickness of 0.004 inch. The resulting photosensitive and thermosensitive element is exposed to light behind a graphic test object and then processed by heating to C. Strong images are obtained as shown in the following table.

TABLE V Ex. Activator-toner sec. Image Fog Tone None 1 Dense Low Brown. 36 Phthalazinone 2 Very dense Low Black. 37 Phthallnlide 2 do Low D0.

The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected withing the spirit and scope of the invention.

What is claimed is:

1. In a photographic silver halide processing composition comprising a silver halide developing agent and an alkaline development activator, the improvement comprising an amino hydroxy cycloalkenone silver halide develo ping agent having the formula:

wherein R and R are each hydrogen, alkyl containing 1 to 5 carbon atoms, or taken together are atoms completing a 5 or 6 member heterocyclic nucleus; R and R are each hydrogen or alkyl containing 1 to 5 carbon atoms; n is 1 or 2.

2. A photographic silver halide processing composition as in claim 1 comprising an aqueous alkaline silver halide developer solution having a pH of at least about 8.0.

3. A photographic silver halide processing composition as in claim 1 wherein the amino hydroxy cycloalkenone silver halide developing agent is 2-hydroxy-3-morpholino-2-cyclohexenone,

2-hydroxy-3-piperidino-2-cyclohexenone, or

Z-hydroxy-3-dimethylamino-2-cyclohexenone.

4. A photographic processing composition as in claim 1 comprising an auxiliary silver halide developing agent.

5. A photographic composition comprising photographic silver halide and an amino hydroxy cycloalkenone silver halide developing agent having the formula:

wherein R and R are each hydrogen, alkyl containing 1 to 5 carbon atoms, or taken together are atoms completing a 5 or 6 member heterocyclic nucleus; R and R are each hydrogen or alkyl containing 1 to 5 carbon atoms; 11 is 1 or 2.

6. A photographic composition as in claim 4 comprising a photographic silver halide emulsion.

7. A photographic composition as in claim 4 comprising photographic silver halide and 2-hydroxy-3-morpholino-2-cyclohexenone,

2-hydroxy-3-piperidino-2-cyclohexenone, or

2-hydroxy-3-dimethylamino-2-cyclohexenone.

wherein R and R are each hydrogen, alkyl containing 1 to carbon atoms, or taken together are atoms completing a 5 or 6 member heterocyclic nucleus; R and R are each hydrogen, or alkyl containing 1 to 5 carbon atoms; 12 is 1 0r 2.

9. A photographic process as in claim 8 comprising developing said latent image in the presence of an auxiliary silver halide developing agent.

10. A photographic process as in claim 8 comprising developing said-latent image in the presence of ammonia.

11. A photographic process as in claim 8 wherein said amino hydroxy cycloalkenone silver halide developing agent is 2-hydroxy-3-morpholino-2-cyclohexenone,

2-hydroxy-3-piperidino-2-cyclohexenone, or

2-hydroxy-3-dimethylamino-2-cyclohexenone.

References Cited UNITED STATES PATENTS 1,937,844 12/1933 Reed 9666.1 2,691,589 10/1954 Hcnn et al. 96-66.1

NORMAN G. TORCHIN, Primary Examiner 20 I. L.GOODROW, Assistant Examiner mg UNITED STATES PATENT OFFICE v CERTIFICATE OF CORRECTION Patent Ne.3, 9 72. Dated eptember 12, 1972 Inventor) Rolf S Gabrielsen and Ismael A, Olivar'es It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 18, line 69, claim 6, "claim L1." should read --olaim 5-;

line 7'1 claim 7, "claim Lt" should read claim 5 Signed and sealed this 13th day of March 1973.

(SEAL) Attest.

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents 

